DE2263881A1 - METHOD OF MANUFACTURING CARVON - Google Patents
METHOD OF MANUFACTURING CARVONInfo
- Publication number
- DE2263881A1 DE2263881A1 DE19722263881 DE2263881A DE2263881A1 DE 2263881 A1 DE2263881 A1 DE 2263881A1 DE 19722263881 DE19722263881 DE 19722263881 DE 2263881 A DE2263881 A DE 2263881A DE 2263881 A1 DE2263881 A1 DE 2263881A1
- Authority
- DE
- Germany
- Prior art keywords
- pinene
- carvone
- hydroxy
- acid
- carvotanacetone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- ULDHMXUKGWMISQ-UHFFFAOYSA-N carvone Chemical compound CC(=C)C1CC=C(C)C(=O)C1 ULDHMXUKGWMISQ-UHFFFAOYSA-N 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 claims description 19
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 18
- 239000005973 Carvone Substances 0.000 claims description 16
- DJOOMNLGIUGRKD-UHFFFAOYSA-N 5-(2-hydroxypropan-2-yl)-2-methylcyclohex-2-en-1-one Chemical compound CC1=CCC(C(C)(C)O)CC1=O DJOOMNLGIUGRKD-UHFFFAOYSA-N 0.000 claims description 12
- DJOOMNLGIUGRKD-MRVPVSSYSA-N 8-Hydroxy-p-menth-6-en-2-one Natural products CC1=CC[C@@H](C(C)(C)O)CC1=O DJOOMNLGIUGRKD-MRVPVSSYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 9
- 235000019253 formic acid Nutrition 0.000 claims description 9
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 150000004965 peroxy acids Chemical class 0.000 description 5
- OMDMTHRBGUBUCO-IUCAKERBSA-N (1s,5s)-5-(2-hydroxypropan-2-yl)-2-methylcyclohex-2-en-1-ol Chemical compound CC1=CC[C@H](C(C)(C)O)C[C@@H]1O OMDMTHRBGUBUCO-IUCAKERBSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001030 gas--liquid chromatography Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229960000230 sobrerol Drugs 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- OMDMTHRBGUBUCO-UHFFFAOYSA-N trans-sobrerol Natural products CC1=CCC(C(C)(C)O)CC1O OMDMTHRBGUBUCO-UHFFFAOYSA-N 0.000 description 2
- SKBXVAOMEVOTGJ-UHFFFAOYSA-N xi-Pinol Chemical compound CC1=CCC2C(C)(C)OC1C2 SKBXVAOMEVOTGJ-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- -1 aliphatic ethers Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- HHTWOMMSBMNRKP-UHFFFAOYSA-N carvacrol Natural products CC(=C)C1=CC=C(C)C(O)=C1 HHTWOMMSBMNRKP-UHFFFAOYSA-N 0.000 description 1
- RECUKUPTGUEGMW-UHFFFAOYSA-N carvacrol Chemical compound CC(C)C1=CC=C(C)C(O)=C1 RECUKUPTGUEGMW-UHFFFAOYSA-N 0.000 description 1
- 235000007746 carvacrol Nutrition 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- WYXXLXHHWYNKJF-UHFFFAOYSA-N isocarvacrol Natural products CC(C)C1=CC=C(O)C(C)=C1 WYXXLXHHWYNKJF-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- NIXKBAZVOQAHGC-UHFFFAOYSA-N phenylmethanesulfonic acid Chemical class OS(=O)(=O)CC1=CC=CC=C1 NIXKBAZVOQAHGC-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/647—Unsaturated compounds containing a keto groups being part of a ring having unsaturation outside the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
- C07C45/66—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by dehydration
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Description
EHOEE-POULENC S.A., Paris/FrankreichEHOEE-POULENC S.A., Paris / France
Die vorliegende Erfindung "betrifft ein Verfahren zur Herstellung von Garvon,ausgehend von oc-Pinen.The present invention "relates to a method of manufacture from Garvon, starting from oc-pinene.
Das Carvon, das als Aroma und als Parfüm verwendet wird, kommt in verschiedenen natürlichen ätherischen ölen vor, wobei es jedoch aus wirtschaftlichen Gründen bevorzugt ist, es industriell ausgehend von leicht zugänglichen und billigen Verbindungen, wie oc-Pinen, herzustellen. In der Literatur ist die Herstellung von verschiedenen Zwischenverbindungen zwischen dem cx-Pinen und dem Carvon, wie des Oxyds des oc-Pinens, des Sobrerols und des 8-Hydroxy-carvotanacetons und die Überführung der einen in die anderen gut beschrieben. Dennoch,sei es aufgrund der Anzahl der Stufen, die deren Kombination umfaßt, sei es aufgrund der Natur der eingesetzten Reaktanten, beispielsweise der Verwendung von Chromsäure zur Oxydation des Sobrerols in 8-Hydroxy-carvotan-The carvone used as a flavor and as a perfume is coming present in various natural essential oils, however, being there for economic reasons it is preferred industrially starting from readily available and cheap compounds such as oc-pinene. In the literature, the preparation of various intermediate compounds between the cx-pinene and the Carvone, such as the oxide of oc-pinene, sobrerol and 8-hydroxy-carvotanacetone and the transition from one to the other is well described. Still, be it because of the number of Levels that include their combination, be it due to nature the reactants used, for example the use of chromic acid to oxidize sobrerol in 8-hydroxy-carvotan
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aceton, gestattet es die Aneinanderkettung dieser verschiedenen Stufen nicht,zu einem industriellen Verfahren zur Überführung von oc-Pinen in das Carvon zu gelangen. Es ist daher besonders wesentlich, ein einfaches Verfahren zur Herstellung von Carvon ausgehend von a-Pinen, zur Verfugung zu. stellen, bei dem nur eine begrenzte Anzahl an Stufen und nicht sehr kostspielige Reaktanten zum Einsatz gelangen.acetone, does not allow these different stages to be chained together to form an industrial process to get from oc-pinene into the carvone. It is therefore particularly essential to have a simple process for making carvone starting from a-pinene, available too. provide a limited number of stages and not very costly reactants get used.
Erfindungsgemäß wurde nun ein einfaches und ökonomisches Verfahren, zur Herstellung des Carvons, ausgehend von a-Pinen, gefunden, das darin besteht, daß man 8-Hydroxy-carvotanaceton herstellt und dieses anschließend auf an sich bekannte Weise in Carvon überführt,und das dadurch gekennzeichnet ist, daß man das 8-Hydroxy-carvotanaceton direkt durch Oxydation von a-Pinen mit Perameisensäure, die in einer Menge von zumindest 1,5 Mol je Mol a-Pinen verwendet wird, herstellt.According to the invention, a simple and economical process has now been for the preparation of the carvone, starting from a-pinene, found, which consists in that 8-hydroxy-carvotanacetone and this is then converted into carvone in a manner known per se, and which is characterized in that the 8-Hydroxy-carvotanacetone directly by oxidation of a-pinene with performic acid, which in an amount of at least 1.5 moles each Mol a-pinene is used.
Die Oxydation von a-Pinen in 8-Hydroxy-carvotanaceton durch Perameisensäure kann in Gegenwart oder in Abwesenheit eines unter den Reaktionsbedingungen inerten Lösungsmittels durchgeführt werden. Man kann Ameisensäure, die aliphatischen Äther (Dimethyläther, Diäthyläther), einen halogenierten Kohlenwasserstoff (Chloroform, 1,2-Dichloräthan, Chlorbenzol), einen cycloaliphatischen Kohlenwasserstoff (Cyclohexan) oder einen aromatischen Kohlenwasserstoff (Benzol, Toluol) verwenden.The oxidation of a-pinene in 8-hydroxy-carvotanacetone by performic acid can be carried out in the presence or absence of a solvent which is inert under the reaction conditions. One can use formic acid, the aliphatic ethers (dimethyl ether, Diethyl ether), a halogenated hydrocarbon (chloroform, 1,2-dichloroethane, chlorobenzene), a cycloaliphatic Use a hydrocarbon (cyclohexane) or an aromatic hydrocarbon (benzene, toluene).
Die Perameisensäure kann als solche in zuvor gebildetem Zustand in Form einer Lösung in Ameisensäure verwendet werden, oder "in situ" durch Umsetzung von Wasserstoffperoxyd mit Ameisensäure nach bekannten Methoden hergestellt werden. Für das molare Verhältnis von Perameisensäure zu a-Pinen gibt es keine obere kritische Grenze. Im allgemeinen ist es nicht erforderlich, mehr als 2,5 Mole Persäure je Mol Kohlenwasserstoff einzusetzen. ManPerformic acid can be used as such in a previously formed state can be used in the form of a solution in formic acid, or "in situ" by reacting hydrogen peroxide with formic acid be produced by known methods. There is no upper critical one for the molar ratio of performic acid to a-pinene Border. In general, it is not necessary to use more than 2.5 moles of peracid per mole of hydrocarbon. Man
309827/1156309827/1156
arbeitet vorzugsweise mit 1,8 bis 2,2 Mol Persäure je Mol a-Pinen.works preferably with 1.8 to 2.2 moles of peracid per mole of a-pinene.
Die Temperatur der Oxydationsphase kann zwischen 0 und 700C, und vorzugsweise zwischen 10 und 400C variieren. Diese Phase wird auf einfache Weise, entweder durch Einbringen von Persäure ( oder von Wasserstoffperoxyd und Ameisensäure) in gegebenenfalls in Lösung vorliegendes oc-Pinen oder durch Einbringen von a-Pinen in Persäure hergestellt.The temperature of the can Oxydationsphase between 0 and 70 0 C, and preferably vary between 10 and 40 0 C. This phase is produced in a simple manner, either by introducing peracid (or hydrogen peroxide and formic acid) into oc-pinene, which may be in solution, or by introducing a-pinene into peracid.
Das erfindungsgemäße Verfahren kann auf racemisches a-Pinen oder auf dessen optische Isomeren angewendet werden.The inventive method can be based on racemic a-pinene or can be applied to its optical isomers.
Die überführung von 8-Hydroxy-carvotanaceton in Carvon kann nach üblichen Methoden durchgeführt werden. So kann man das Hydroxyketon in Gegenwart einer starken Mineralsäure, wie der Schwefel- oder Phosphorsäure oder einer Sulfonsäure (Benzol- und Toluol-Sulfonsäuren) oder in Gegenwart von Oxalsäure dehydratisieren. Man kann auch das 8-Hydroxy-carvotanaceton mittels einer niedrigen aliphatischen Säure (beispielsweise Essigsäure) verestern und dann die hergestellten Ester pyrolisieren (siehe . hierzu US-Patentschrift 2 796 428).The conversion of 8-hydroxy-carvotanacetone into carvone can be carried out according to conventional methods. So you can the hydroxyketone in the presence of a strong mineral acid, such as the Sulfuric or phosphoric acid or a sulphonic acid (benzene and toluene sulfonic acids) or dehydrate in the presence of oxalic acid. You can also use the 8-hydroxy-carvotanacetone a low aliphatic acid (e.g. acetic acid) esterify and then pyrolize the esters produced (see. US Pat. No. 2,796,428).
Unabhängig von der Art des in Betracht gezogenen Verfahrens, „ kann das 8-Hydroxy-carvotanaceton zuvor vom Oxydationsmilieu des oc-Pinens abgetrennt werden, oder auch in diesem Reaktionsmilieu behandelt werden. Ein wegen seiner Einfachheit der Durchführung bevorzugtes Verfahren besteht darin, eine starke Säure zu dem Oxydationsmilieu des oc-Pinens hinzuzufügen und die Dehydratation des 8-Hydroxy-carvotanacetons durch Erwärmen (beispielsweise zwischen 40 und 2000C), wobei das Carvonnach Maßgabe seiner Bildung destilliert, durchzuführen.Regardless of the type of process being considered, “the 8-hydroxy-carvotane acetone can be separated from the oxidation medium of the oc-pinene beforehand, or it can also be treated in this reaction medium. A preferred because of its simplicity of implementation method is to add a strong acid to the Oxydationsmilieu of oc-pinene and the dehydration of the 8-hydroxy-carvotanacetons by heating (for example, between 40 and 200 0 C), wherein the Carvonnach proviso its formation distilled to perform.
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Die folgenden Beispiele erläutern die Erfindung.The following examples illustrate the invention.
Man beschickt einen 200 cm Dreihalskolben, der mit einem Thermometer, einem Tropftrichter, einer Rührvorrichtung und einem Kühlungssystem versehen ist, mit 1000cnr wasserfreiem Äther und 1010 g einer Perameisensäurelösung in wasserfreier Ameisensäure, die durch zweistündige Umsetzung bei Raumtemperatur von 920 g wasserfreier Ameisensäure mit 98,5 g 69 Gew.-%igem Wasserstoffperoxyd (diese Lösung enthält 1,71 Mol Perameisensäure) erhalten wurde. Man beläßt den Kolbeninhalt bei 200C,während man unter Rühren während 25 Minuten 115 »5 g (0,85 Mol) a-Pinen ([a]yj= -460C) hinzufügt. Nach drei Stunden verbleiben unter diesen Bedingungen weniger als 10 % des. anfänglichen wirksamen Sauerstoffs. A 200 cm three-necked flask equipped with a thermometer, a dropping funnel, a stirrer and a cooling system is charged with 1000 cnr anhydrous ether and 1010 g of a performic acid solution in anhydrous formic acid, which is obtained by reacting 920 g of anhydrous formic acid with 98, 5 g of 69% strength by weight hydrogen peroxide (this solution contains 1.71 mol of performic acid) was obtained. It leaves the contents of the flask at 20 0 C, while adding, with stirring for 25 minutes 115 »5 g (0.85 mole) of a-pinene ([a] yj = -46 0 C). After three hours, less than 10 % of the initial effective oxygen remains under these conditions.
Man vertreibt den Äther und die Ameisensäure durch Destillation im Vakuum unter Wasserbadtemperatur. Man gewinnt einen Rückstand, der 283 g wiegt, und in dem kein a-Pinen mehr verblieben ist (Umwandlungsgrad 100%), und der 25,8 g 8-Hydroxy-carvotanaceton enthält, welches durch Gasflüssigkeitschromatographie bestimmt wurde, entsprechend einer Ausbeute in bezug auf eingesetztes a-Pinen von 18 %. Das 2,4-D.initrophenylhydrazon einer Probe des 8-Hydroxy-carvotanacetons, das durch Destillation .isoliert wurde, schmilzt bei 199°C (gemessen auf dem Kofier-Block)*The ether and the formic acid are driven off by distillation in vacuo at water bath temperature. A residue is obtained which weighs 283 g and in which no more a-pinene has remained (degree of conversion 100%) and which contains 25.8 g of 8-hydroxy-carvotanacetone, which was determined by gas-liquid chromatography , corresponding to a yield in relation to on a-pinene used of 18%. The 2,4-dinitrophenylhydrazone of a sample of 8-hydroxy-carvotanacetone, which was isolated by distillation, melts at 199 ° C (measured on the Kofier block) *
Man fügt 0,6 Gew.-% p-Toluolsulfonsäure zur Gesamtmenge des Rückstandes hinzu und unterwirft diesen einer Destillation unter einem Druck von 10 bis 20 mm Quecksilber. Man erhält so 227 g einer Fraktion, die zwischen 30 und 158°C destilliert, und in der man durch Gasflüssigkeitschromatographie die folgenden Komponenten bestimmt:0.6% by weight of p-toluenesulfonic acid is added to the total amount of des The residue is added and subjected to distillation under a pressure of 10 to 20 mm of mercury. This gives 227 g a fraction distilled between 30 and 158 ° C and in which, by gas-liquid chromatography, the following Components determined:
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7,4- Gew.-% Carvon
6,3 % Carvacrol7.4 wt% carvone
6.3 % carvacrol
1.8 Gew.-% e-Hydroxy-carvotanaceton1.8% by weight of e-hydroxy-carvotane acetone
3.9 Gew.-% Pinol und3.9 wt .-% Pinol and
2,4- Gew.-% oc-Camphol-aldehyd.2.4 wt% oc-camphol aldehyde.
Das erhaltene Destillat wird darauf einer erneuten Destillation im Vakuum von 10 bis 20 mm unterworfen und anschließend rektifiziert. Man erhält auf diese Weise 16,5 g Carvon, das die folgenden Eigenschaften aufweist:The distillate obtained is then subjected to renewed distillation in a vacuum of 10 to 20 mm and then rectified. In this way 16.5 g of carvone are obtained, which has the following properties:
= 101,5 - 102°C;= 101.5-102 ° C;
njp = 1,496}
[oüD = -64°;njp = 1.496}
[ou D = -64 °;
Schmelzpunkt des 2,4—Dinitrophenylhydrazons: 1890C.Melting point of the 2,4-dinitrophenylhydrazone: 189 ° C.
Die Ausbeute an Carvon in bezug auf eingesetztes a-Pinen beträgtThe yield of carvone based on the α-pinene used is
■z■ z
Man beschickt einen 1000 cm Kolben, der wie in Beispiel 1 ausgerüstet ist, mit 54·,4- g α-Einen. (0,4-0 Mol), und fügt dann nach Abkühlen des Kolbeninhalts auf 100C fortschreitend während 80 Minuten 435 g einer Lösung von Perameisensäure, die wie in Beispiel 1 hergestellt wurde (entsprechend o,8 Mol Persäure), hinzu. Die Temperatur steigt auf 700C an und wird dann auf 200C zurückgeführt. Man beläßt zwei Stunden unter diesen Bedingungen. Es verbleiben dann nur noch 2 % an aktivem Sauerstoff in dem Kolben. Man vertreibt den größeren Teil der Ameisensäure durch Destillation unter Vakuum. Man bestimmt 12,1 g 8-Hydroxy-carvotanaceton in dem Rückstand (Ausbeute 18 % in bezug auf eingesetztes a-Pinen). Der Rückstand wird darauf wie in Beispiel 1A 1000 cm flask equipped as in Example 1 is charged with 54.4 g of α-units. (0.4 to 0 mol), and then added after cooling the flask contents at 10 0 C gradually over 80 minutes 435 g of a solution of performic acid, which was prepared as in Example 1 (corresponding o, 8 moles of peracid) added. The temperature rises to 70 0 C and is then returned to 20 0 C. It is left under these conditions for two hours. Only 2 % of active oxygen then remains in the flask. The greater part of the formic acid is driven off by distillation under vacuum. 12.1 g of 8-hydroxy-carvotanacetone are determined in the residue (yield 18 % based on the α-pinene used). The residue is then as in Example 1
309827/1156309827/1156
behandelt. Die Ausbeute an isoliertem Carvon beträgt 13 % in bezug auf eingesetztes ot-Pinen.treated. The yield of isolated carvone is 13 % based on the ot-pinene used.
309827/1156309827/1156
Claims (3)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7146988A FR2166505A5 (en) | 1971-12-28 | 1971-12-28 | Carbone from alpha-pinene - by oxidn with performic acid to hydroxy-8-carvotanacetone and dehydration |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2263881A1 true DE2263881A1 (en) | 1973-07-05 |
Family
ID=9088220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19722263881 Pending DE2263881A1 (en) | 1971-12-28 | 1972-12-28 | METHOD OF MANUFACTURING CARVON |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS4875546A (en) |
| BE (1) | BE793364A (en) |
| CH (1) | CH546723A (en) |
| DE (1) | DE2263881A1 (en) |
| FR (1) | FR2166505A5 (en) |
| IT (1) | IT973066B (en) |
| NL (1) | NL7217386A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0077682A1 (en) * | 1981-10-21 | 1983-04-27 | Pfizer Limited | Microbiological process for the preparation of 1-carvone |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5651386Y2 (en) * | 1975-07-31 | 1981-12-01 | ||
| KR101726730B1 (en) | 2012-12-03 | 2017-04-13 | 도쿄하쿠젠 가부시키가이샤 | Cremation system |
-
1971
- 1971-12-28 FR FR7146988A patent/FR2166505A5/en not_active Expired
-
1972
- 1972-12-20 NL NL7217386A patent/NL7217386A/xx unknown
- 1972-12-26 JP JP12965672A patent/JPS4875546A/ja active Pending
- 1972-12-27 BE BE793364D patent/BE793364A/en unknown
- 1972-12-27 CH CH1888772A patent/CH546723A/en not_active IP Right Cessation
- 1972-12-28 IT IT3375972A patent/IT973066B/en active
- 1972-12-28 DE DE19722263881 patent/DE2263881A1/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0077682A1 (en) * | 1981-10-21 | 1983-04-27 | Pfizer Limited | Microbiological process for the preparation of 1-carvone |
Also Published As
| Publication number | Publication date |
|---|---|
| IT973066B (en) | 1974-06-10 |
| BE793364A (en) | 1973-06-27 |
| FR2166505A5 (en) | 1973-08-17 |
| JPS4875546A (en) | 1973-10-11 |
| NL7217386A (en) | 1973-07-02 |
| CH546723A (en) | 1974-03-15 |
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